CN103066244A - Preparation method of vanadium oxide nanocomposite of lithium ion battery - Google Patents
Preparation method of vanadium oxide nanocomposite of lithium ion battery Download PDFInfo
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- CN103066244A CN103066244A CN2012105219406A CN201210521940A CN103066244A CN 103066244 A CN103066244 A CN 103066244A CN 2012105219406 A CN2012105219406 A CN 2012105219406A CN 201210521940 A CN201210521940 A CN 201210521940A CN 103066244 A CN103066244 A CN 103066244A
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- barium oxide
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- carbon nanotube
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a vanadium oxide nanocomposite of a lithium ion battery and a preparation method thereof. The preparation method comprises weighing sucrose, concentrated sulfuric acid, water and a silica template, and roasting to obtain porous carbon nanotube; adding ammonium metavanadate into a polyvinyl alcohol aqueous solution and performing an electrospinning to obtain vanadium oxide nano-materials; mixing the vanadium oxide nano-materials and hydrogen peroxide and reacting to form a vanadium oxygen sol; performing a reflux for the porous carbon nanotube with the concentrated sulfuric acid and adding into the vanadium oxygen sol; and performing a hydro-thermal reaction for black colloidal suspension to obtain the vanadium oxide nanometer/carbon composite material. By uniformly distributing the vanadium oxide nano-material inside and outside the porous carbon nanotube, the prepared vanadium oxide nanometer/carbon composite material is stable in structure, and uniform in distribution, and thus has a high energy density and a stable cyclic performance, and when used as cathode materials of the lithium ion battery, is high in specific capacity and long in service life.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery electrode material, relate in particular to a kind of lithium ion battery barium oxide nano composite material and preparation method thereof.
Background technology
The trend of electronic apparatus miniaturization, energetic, portability, development and the exploitation of the development of space technology and the demand of defence equipment and electric automobile have higher requirement to the performance of lithium ion battery.And the improvement of performance of lithium ion battery depends primarily on the raising of embedding lithium electrode material energy density and cycle life.
Present commercial lithium ion battery adopts lithium transition-metal oxide/graphite system as negative active core-shell material mostly, although the chemical property of this class system is excellent, but it is lower itself to store up the lithium ability, particularly the theoretical capacity of carbon class negative active core-shell material only is 372 MAh/gs, and so low capacity has been difficult to adapt to the miniaturization development of various portable electric appts and electric automobile at present to the demand of large capacity, high power chemical power source.
V
2O
5Material is because its special layer structure makes it than other conventional cathode material (LiMn
2O
4, LiCoO
2And LiFePO
4Deng) have a larger specific capacity.But because the unsteadiness of its structure makes it be difficult to drop into commercial the application.
Summary of the invention
For overcoming the problems referred to above, the invention provides a kind of lithium ion battery preparation method of barium oxide nano composite material, when the anode material that uses the method to prepare is used for lithium ion battery, when having larger specific capacity, Stability Analysis of Structures, good cycle.
To achieve these goals, a kind of lithium ion battery provided by the invention comprises the steps: with the preparation method of barium oxide nano composite material
Step 1, preparation porous carbon nanotube
According to weight ratio 1: (0.1-0.15): (1-10): (0.5-2) take by weighing sucrose, the concentrated sulfuric acid, water and template silicon dioxide, mix post-drying;
With mixture roasting under inert gas shielding: heating rate is for per hour heating up 50-80 ℃, and temperature rises to 500-700 ℃, keeps 4-7 hour;
Remove template silicon dioxide, obtain the inner porous carbon nanotube of nano hollow carbon pipe that is;
Step 2, preparation barium oxide nano material
By mass parts, 1-2 part polyvinyl alcohol is joined in 10-15 part distilled water, be incubated 3-4h after being heated to 85-100 ℃, be cooled to the polyvinyl alcohol water solution that room temperature obtains clear, 0.5-1 part ammonium metavanadate is joined in the polyvinyl alcohol water solution for preparing, be heated to 70-80 ℃ of insulation 6-7h, be cooled to the barium oxide precursor sol that room temperature obtains a kind of yellow, clear;
The precursor sol that obtains injects the shower nozzle of electric spinning machine, take conductive substrate as collecting electrode, adopt the accelerating voltage of 20-25kV to prepare by the compound nano wire of barium oxide and polyvinyl alcohol, the nano wire that obtains is at 500-550 ℃ of insulation 2-4h, be cooled to room temperature, obtain yellow barium oxide nano material;
Step 3, preparation barium oxide nanometer/carbon composite
Be that 35% hydrogen peroxide mixes with barium oxide nano material and mass concentration, form vanadium oxygen colloidal sol after the reaction, wherein: the mass volume ratio of barium oxide and hydrogen peroxide is 1: 20-1: 50 (g/ml);
Above-mentioned porous carbon nanotube carbon is used red fuming nitric acid (RFNA) 60-80 ℃ of backflow 1-2 hour;
Porous carbon nanotube after refluxing is joined fully stirring in the described vanadium oxygen colloidal sol, until form the gluey suspension-turbid liquid of black;
With the gluey suspension-turbid liquid hydro-thermal reaction of black 2-4 days, namely get barium oxide nanometer/carbon composite.
Wherein, in the step 1, before described oven dry, mixture uniform stirring 3-6 hour.
Wherein, in the step 1, described oven dry is: heating rate is for per hour heating up 10-20 ℃, and temperature rises to 150-200 ℃, keeps 3-8 hour.
Wherein, in the step 1, the method for removing silicon dioxide is: the mixture after the roasting is put into potassium hydroxide stirred 10-15 hour, make the silica template dissolving, then filter, wash, drying.
Wherein, in the step 2, described conductive substrate can be copper/aluminum foil material, is preferably the aluminium foil conductive substrate.
Wherein, in the step 3, described hydrothermal temperature is 100-300 ℃.
The present invention also provides a kind of lithium ion battery barium oxide nano composite material of said method preparation.
Barium oxide nanometer/the carbon composite of the present invention's preparation, by special process the barium oxide nano material is evenly distributed on inside and outside the porous carbon nanotube, so that the Stability Analysis of Structures of composite material and being uniformly dispersed, therefore possessing outside the high energy density, also has stable cycle performance, during as lithium ion battery negative material, specific capacity is high, long service life.
Embodiment
Embodiment one
Preparation porous carbon nanotube
According to weight ratio 1: 0.1: 2: 0.5 took by weighing sucrose; the concentrated sulfuric acid and water and template silicon dioxide; uniform stirring is 3 hours after mixing; mixture is put into baking oven; the baking oven heating rate is for per hour heating up 10 ℃; temperature rises to 150 ℃, keeps 8 hours, after the solvent evaporation; mixture is put into the pyroreaction still roasting of inert gas shielding; pyroreaction still heating rate is for per hour heating up 50 ℃, and temperature rises to 500 ℃, keeps 7 hours; mixture after the roasting is put into potassium hydroxide to be stirred 10 hours; make the silica template dissolving, then filter; washing; drying obtains the inner porous carbon nanotube of nano hollow carbon pipe that is.
Preparation barium oxide nano material
By mass parts, 1 part of polyvinyl alcohol is joined in 10 parts of distilled water, magnetic agitation is incubated 4h after being heated to 85 ℃, naturally cool to the polyvinyl alcohol water solution that room temperature obtains clear, 0.5 part of ammonium metavanadate is joined in the polyvinyl alcohol water solution for preparing, magnetic agitation is heated to 70 ℃ of insulation 7h, be cooled to room temperature and obtain a kind of yellow, the barium oxide precursor sol of clear, the precursor sol that obtains injects the shower nozzle of electric spinning machine, take the aluminium foil conductive substrate as collecting electrode, adopt the accelerating voltage of 20kV to prepare by the compound nano wire of barium oxide and polyvinyl alcohol, the nano wire that obtains is put into resistance furnace, at 500 ℃ of insulation 2h, naturally cool to room temperature, obtain yellow barium oxide nano material.
Preparation barium oxide nanometer/carbon composite
Be that 35% hydrogen peroxide mixes with barium oxide nano material and concentration, form barium oxide colloidal sol behind the vigorous reaction, wherein: the mass volume ratio of barium oxide and hydrogen peroxide is 1:20 (g/ml); Above-mentioned porous carbon nanotube carbon was refluxed 2 hours with 60 ℃ of red fuming nitric acid (RFNA)s; Porous carbon nanotube after refluxing is joined fully stirring in the described barium oxide colloidal sol, until form the gluey suspension-turbid liquid of black; The gluey suspension-turbid liquid of black is moved into hydrothermal reaction kettle, again reactor is placed temperature control box, through 2 days hydro-thermal reactions, namely get barium oxide nanometer/carbon composite.
Embodiment two
Preparation porous carbon nanotube
According to weight ratio 1: 0.15: 10: 2 took by weighing sucrose; the concentrated sulfuric acid and water and template silicon dioxide; uniform stirring is 6 hours after mixing; mixture is put into baking oven; the baking oven heating rate is for per hour heating up 20 ℃; temperature rises to 200 ℃, keeps 3 hours, after the solvent evaporation; mixture is put into the pyroreaction still roasting of inert gas shielding; pyroreaction still heating rate is for per hour heating up 80 ℃, and temperature rises to 700 ℃, keeps 4 hours; mixture after the roasting is put into potassium hydroxide to be stirred 15 hours; make the silica template dissolving, then filter; washing; drying obtains the inner porous carbon nanotube of nano hollow carbon pipe that is.
Preparation barium oxide nano material
By mass parts, 2 parts of polyvinyl alcohol are joined in 15 parts of distilled water, magnetic agitation is incubated 3h after being heated to 100 ℃, naturally cool to the polyvinyl alcohol water solution that room temperature obtains clear, 1 part of ammonium metavanadate is joined in the polyvinyl alcohol water solution for preparing, magnetic agitation is heated to 80 ℃ of insulation 6h, be cooled to room temperature and obtain a kind of yellow, the barium oxide precursor sol of clear, the precursor sol that obtains injects the shower nozzle of electric spinning machine, take the aluminium foil conductive substrate as collecting electrode, adopt the accelerating voltage of 25kV to prepare by the compound nano wire of barium oxide and polyvinyl alcohol, the nano wire that obtains is put into resistance furnace, at 550 ℃ of insulation 2h, naturally cool to room temperature, obtain yellow barium oxide nano material.
Preparation barium oxide nanometer/carbon composite
Be that 35% hydrogen peroxide mixes with barium oxide nano material and concentration, form barium oxide colloidal sol behind the vigorous reaction, wherein: the mass volume ratio of barium oxide and hydrogen peroxide is 1:50 (g/ml); Above-mentioned porous carbon nanotube carbon was refluxed 1 hour with 80 ℃ of red fuming nitric acid (RFNA)s; Porous carbon nanotube after refluxing is joined fully stirring in the described barium oxide colloidal sol, until form the gluey suspension-turbid liquid of black; The gluey suspension-turbid liquid of black is moved into hydrothermal reaction kettle, again reactor is placed temperature control box, through 4 days hydro-thermal reactions, namely get barium oxide nanometer/carbon composite.
Comparative example
The 0.8g polyvinyl alcohol is joined in the 10mL deionized water, be incubated 5h after being heated to 90 ℃ with magnetic stirring apparatus, naturally cool to the polyvinyl alcohol water solution that room temperature obtains clear; The 0.1g ammonium metavanadate is joined in the polyvinyl alcohol water solution for preparing, and magnetic agitation is heated to 90 ℃ of insulation 5h, is cooled to the barium oxide precursor sol that room temperature obtains a kind of yellow, clear; The precursor sol that obtains is injected the shower nozzle of electric spinning machine, take the aluminium foil conductive substrate as collecting electrode, adopt the accelerating voltage of 10-30kV to prepare barium oxide and polyvinyl alcohol nano line; The nano wire that obtains is put into resistance furnace, at 400 ℃ of insulation 0.5h, naturally cools to room temperature, obtains yellow vanadium oxide overlong nanowire.
Take diameter as 18 millimeters, weight as the metal lithium sheet of 0.4 gram as positive active material, take the modified polypropene barrier film as barrier film, with the LiPF of 1 mol/L
6Solution/(solvent is 1: 1 EC of volume ratio: the DMC mixed solvent) be electrolyte, the vanadium oxide overlong nanowire that is made by above-described embodiment one, barium oxide nanometer/carbon composite of two and comparative example take 0.05 gram respectively is as negative electrode active material, negative active core-shell material in mass ratio: polytetrafluoroethylene: be coated in equably behind acetylene black=80:10:10 mixed grinding and do negative pole on the copper mesh, make 2016 type button cells.Be to carry out electric performance test under 25 ℃ at probe temperature, after tested this embodiment one with two material compare with the material of comparative example, first discharge specific capacity has promoted more than the 30-40%, cycle life improves more than 3 times.
Above specific embodiments of the invention are described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, not breaking away from impartial conversion and the modification of doing under the spirit and scope of the present invention, all should contain within the scope of the invention.
Claims (7)
1. the preparation method of a lithium ion battery usefulness barium oxide nano composite material is characterized in that, comprises the steps:
Step 1, preparation porous carbon nanotube
According to weight ratio 1: (0.1-0.15): (1-10): (0.5-2) take by weighing sucrose, the concentrated sulfuric acid, water and template silicon dioxide, mix post-drying;
With mixture roasting under inert gas shielding: heating rate is for per hour heating up 50-80 ℃, and temperature rises to 500-700 ℃, keeps 4-7 hour;
Remove template silicon dioxide, obtain the inner porous carbon nanotube of nano hollow carbon pipe that is;
Step 2, preparation barium oxide nano material
By mass parts, 1-2 part polyvinyl alcohol is joined in 10-15 part distilled water, be incubated 3-4h after being heated to 85-100 ℃, be cooled to the polyvinyl alcohol water solution that room temperature obtains clear, 0.5-1 part ammonium metavanadate is joined in the polyvinyl alcohol water solution for preparing, be heated to 70-80 ℃ of insulation 6-7h, be cooled to the barium oxide precursor sol that room temperature obtains a kind of yellow, clear;
The precursor sol that obtains injects the shower nozzle of electric spinning machine, take conductive substrate as collecting electrode, adopt the accelerating voltage of 20-25kV to prepare by the compound nano wire of barium oxide and polyvinyl alcohol, the nano wire that obtains is at 500-550 ℃ of insulation 2-4h, be cooled to room temperature, obtain yellow barium oxide nano material;
Step 3, preparation barium oxide nanometer/carbon composite
Be that 35% hydrogen peroxide mixes with barium oxide nano material and mass concentration, form vanadium oxygen colloidal sol after the reaction, wherein: the mass volume ratio of barium oxide and hydrogen peroxide is 1: 20-1: 50 (g/ml);
Above-mentioned porous carbon nanotube carbon is used red fuming nitric acid (RFNA) 60-80 ℃ of backflow 1-2 hour;
Porous carbon nanotube after refluxing is joined fully stirring in the described vanadium oxygen colloidal sol, until form the gluey suspension-turbid liquid of black;
With the gluey suspension-turbid liquid hydro-thermal reaction of black 2-4 days, namely get barium oxide nanometer/carbon composite.
2. method according to claim 1 is characterized in that, in the step 1, and before described oven dry, mixture uniform stirring 3-6 hour.
3. method according to claim 1 and 2 is characterized in that, in the step 1, described oven dry is: heating rate is for per hour heating up 10-20 ℃, and temperature rises to 150-200 ℃, keeps 3-8 hour.
4. method according to claim 1 is characterized in that, in the step 1, the method for removing silicon dioxide is: the mixture after the roasting is put into potassium hydroxide stirred 10-15 hour, make the silica template dissolving, then filter, wash, drying.
5. method according to claim 1 is characterized in that, in the step 2, described conductive substrate is the aluminium foil conductive substrate.
6. method according to claim 1 is characterized in that, in the step 3, described hydrothermal temperature is 100-300 ℃.
7. lithium ion battery barium oxide nano composite material of method preparation as claimed in claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707301A (en) * | 2019-09-05 | 2020-01-17 | 珠海恒力源机电有限公司 | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof |
| CN110838583A (en) * | 2019-12-10 | 2020-02-25 | 华中科技大学 | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery |
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| CN101841036A (en) * | 2010-05-26 | 2010-09-22 | 耿世达 | Multi-sulfur carbon nanofiber composite cathode material for lithium ion battery and manufacturing method |
| CN101857193A (en) * | 2010-06-01 | 2010-10-13 | 武汉理工大学 | Vanadium oxide overlong nanowire with hierarchic structure and preparation method thereof |
| CN102244255A (en) * | 2011-05-26 | 2011-11-16 | 同济大学 | Novel cathode material of vanadium oxide nanometer lithium ion battery and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101841036A (en) * | 2010-05-26 | 2010-09-22 | 耿世达 | Multi-sulfur carbon nanofiber composite cathode material for lithium ion battery and manufacturing method |
| CN101857193A (en) * | 2010-06-01 | 2010-10-13 | 武汉理工大学 | Vanadium oxide overlong nanowire with hierarchic structure and preparation method thereof |
| CN102244255A (en) * | 2011-05-26 | 2011-11-16 | 同济大学 | Novel cathode material of vanadium oxide nanometer lithium ion battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707301A (en) * | 2019-09-05 | 2020-01-17 | 珠海恒力源机电有限公司 | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof |
| CN110838583A (en) * | 2019-12-10 | 2020-02-25 | 华中科技大学 | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery |
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Application publication date: 20130424 |